oil sands products spill response studies at environment...

Oil Sands Products Spill Response Studies

at Environment Canada Emergencies Science and Technology Section

Environment Canada Ottawa, ON

National Academy of Sciences Washington D.C.

9 March 2015

NAS, Wash. D.C., 9 March 2015 page 2

Oil Sands Products Spill Response Studies

Goal: Supply the knowledge responders need to prepare for, and respond to marine

spills

Four pillars: 1.  Identify Spill Hazards 2.  Assess Environmental Vulnerabilities 3.  Develop Risk Assessment tools 4.  Test Response Tools


Joint Federal Project

•  Environment Canada •  Fisheries and Oceans Canada •  Natural Resources Canada


Identify Spill Hazards

•  Oil sands product composition and properties –  Physical bulk properties: density, viscosity, flashpoint, vapour pressure –  Chemical Composition: Groups (“SARA”, CCME), Analytes (n-Alkanes,

PAH, aPAH, “biomarkers”) –  Develop forensic markers/toolbox for identification of oil sands products –  Lead: B. Hollebone, WS&T

•  Fate and Behaviour studies –  Weathering/Buoyancy (lab simulations, meso-scale, shoreline microcosm) –  Evaporation, Dissolution and Emulsification –  Photo-oxidation and oil breakdown –  Sedimentation and oil-aggregate formation –  Leads: B. Hollebone, A. Khelifa WS&T

•  Health and safety information for responders –  Development of guidebook for Responder H&S for oil sands product spills. –  Leads: P. Lambert, WS&T


Hazards: Oil Sands Products Composition and Properties Develop database of oil sands products composition and properties to support operational modelling and response

Degree of Evaporation (Mass Loss w/w%) Fresh (0%)

W1 (8.5%)

W2 (16.9%)

W3 (25.3%)

W4 (26.5%)

Sulphur Content (% w/w) 3.0 4.1 4.5 4.9 4.8 Water Content (% w/w) 1.5 0.9 0.2 0.0 0.0 Flash Point (°C) < -5 < -5 29 159 173 Pour Point (°C) < -25 < -25 -6 24 33 Density (g/mL) 0°C 0.9399 0.9646 0.9949 1.0214 1.0211

15°C 0.9253 0.9531 0.9846 1.0127 1.0140 20°C 0.9148 0.9547*

API Gravity 20.9 16.6 12.0 8.2 8.0 Dynamic Viscosity 0°C 1.30E+03 9.82E+03 2.04E+05 9.35E+07 >1.00E+08 (mPa•s) 15°C 347 1.72E+03 2.97E+04 2.52E+05 7.91E+06

40°C 59.8 348* Emulsion Formation Stability Class Entrained Entrained Entrained Entrained DNF Tendency and Stability Complex Modulus (Pa) 44.6 89.7 467 1.26E+04 N/A

Water Content (%w/w) 40 35 33 6 N/A Surface Tension 0°C 31.2 31.9 NM NM NM (Air/Oil, mN/m) 15°C 30.2 31.1 31.2 NM NM

20°C 27.5 Interfacial Tension 0°C 24.8 NM NM NM NM (Oil/Water, mN/m) 15°C 24.2 28.0 NM NM NM Interfacial Tension 0°C 25.0 NM NM NM NM (Oil/33‰ Brine, mN/m) 15°C 23.8 26.0 NM NM NM

Access Western Blend (winter) Physical Properties AWB (winter)

aPAH compostion


Hazards: Environmental Forensics

•  Develop protocols for forensic identification of oil and weathered oil –  Essential tool for response and planning, to judge spill extent and

endpoints, to verify identity and quantity of spilled oil. –  Essential tool to enable other research: fate and behaviour, toxicology

•  Relies on unique chemical compositions of oil sands products –  Evaluation of n-Alkanes, PAH/APAH and saturate “biomarkers”

•  Used in real spills –  Enbridge Line 6b, Kalamazoo River, MI –  Exxon-Mobil Pegasus, Mayflower AK

Requires survey of products moved by ship and through pipelines


Top – Spilled product, Mayflower 2013 Bottom – Source Oil, Pegasus pipeline


Hazards: Fate and Behaviour •  Evaluate changes to product properties and composition

induced by environmental weathering: Evaporation, Dissolution, Photo-degradation

•  Examine behaviours of products in the environment as it weathers: Sinking/buoyancy, Emulsification, Dispersion, Sedimentation and oil-aggregate formation

•  Interactions with shorelines in microcosms, adhesion to surfaces, penetration and flushing from simulated beaches

•  Longer-term studies of weathering and behaviour in meso-scale simulators and wave tanks to better quantify longer-term spill fates in more realistic conditions

Work to date indicates that diluted bitumen products have unique behaviours and weathering characteristics


Hazards: Initial dilbit buoyancy studies Conditions Fate Behaviour

•  No sediment •  All weatherings of dilbit

•  Floats as oil-water mixture •  Floats and spreads like thick oil, e.g., Burnaby, BC

•  Suspended fine and medium sediment

•  Fresh to moderate weathering of dilbit

•  Large part of oil sinks as fine oil particles

•  Suspended in water column, sinks, and disperses, e.g., Kalamazoo MI

•  Suspended fine and medium sediment

•  Highly weathered dilbit

•  Floating oil “balls” •  Floats and “balls” can disperse

•  Suspended coarse sediment

•  All weatherings of dilbit

•  Large part of oil floats as water-oil mixture

•  Some sunken oil/sand agglomerations

•  Most oil floats and spreads like thick oil

•  Few oil/sand agglomerations sink


Submerged and Sunken Dilbit

Fresh Light evaporation Moderate evaporation

Dilbit mixed with high concentration of fine sediment for 8 hours, allowed to settle for 24 hours

(15 °C, sea water---3.3% salt, Access Western Blend oil)


Evaluation of Density and particle size

Density evaluation using mixtures of water: ethylene glycol for settled layer of CLB Winter Fresh in saltwater: kaolin mixture. The 60:40 water: ethylene glycol is considered as transition point

Oil Oil 15 ºC (g/cm3)

Density of oil-kaolin (1-2 µm)

Oil-DC benthic sediment (2-60 µm)

Cold Lake (winter), Fresh 0.925 (Emulsion-Meso)

1.059 (Disperse-Sink)


Cold Lake (winter), W2, 15.75% weathered

0.982 (Emulsion Entrained)



Cold Lake (winter), W4, 25.2% weathered

1.009 (Emulsion Entrained)

0.999 (Tarballs-Float)

0.999 (Tarballs-Float)

0

2

4

6

8

10

12

0.01 0.1 1 10 100 1000 10000

Volu

me

(%)

Particle size (µm)

Comparison of Particle Size Distribution

natural sediment KA04 CLB fresh ‒ KA04

CLB W2 15.75% ‒ KA04


Floating Oil “Balls”

Highly evaporated dilbit mixed with saltwater and fine sediment

Oil has very high viscosity, similar to native bitumen

Discrete oil “balls” form after mixing (fingernail size)

Floats in seawater

Photos: Access Western Blend, 25% evaporated, 8 hours at 15 °C)


Vulnerability Assessment

•  Identify vulnerable locations near possible shipping routes, including:

–  Human infrastructure, –  Ecologically significant communities, sensitive species, and

habitats, and sensitive shorelines. –  Response requirements: access, and pre-selection of

appropriate response options

•  Initial phases have focussed on the Canadian west coast, future work will expand to cover four designated response areas


Initial Shoreline Studies

•  Objectives –  study the fate and behaviour and cleanup of diluted bitumen on

marine shorelines under various conditions –  deliver operational guidance and scientific information that is

legally defensible and credible to spill responders for shoreline treatment option decisions

•  Literature review of the impacts of bitumen and fuels on marine shorelines

•  Initial aerial shoreline survey of the Douglas and Grenville Channels, BC in 2013 and 2014

•  Lead: P. Lambert, B. Hollebone, WS&T


Shoreline Assessments

•  Shoreline survey of the Douglas and Grenville Channels, BC in 2013 and 2014, by air and boat

•  Additional surveys panned in 2015

•  Shoreline segmentation and classification

•  Shoreline material collection for laboratory studies

•  Collaboration with WCMRC and DFO


Risk Assessment

•  Provide responders with accurate, situation-specific forecasts of spill evolution

–  Predictive numerical modeling capacity to forecast spill evolution and impacts on identified vulnerabilities

•  Work to date: Spill modelling –  Incorporate new databases for oil sands product –  Incorporate new wind and hydrodynamic data –  Simulation of hypothetical spills –  Lead: A Khelifa, WS&T

•  Work to date: Weather and Atmospheric Modelling –  Incorporate improved high resolution wind modeling, including high resolution

atmospheric modeling window centered over Northern BC towards the provision of detailed surface winds and other parameters near the surface.

–  Develop hydrological modeling to support DFO's FVCOM. –  Coupling atmospheric and ocean models. –  Lead: R. Hogue, MSC


Response Tools

•  Evaluate technologies and techniques for Physical and chemical mechanisms that serve to detect, contain, destroy or mitigate spilled petroleum products.

•  Detection –  Portable instruments evaluation and protocol development for in-

sediment shoreline oil and dispersed oil at sea –  Lead: P. Lambert, WS&T

•  Countermeasures –  Dispersant testing fresh/weathered dilbit samples –  Continuing evaluation of dispersant, shoreline-treating agent and

other products –  New protocol development –  Lead: B. Fieldhouse, P. Lambert, WS&T


Response Tools: Detection

•  Oil profiling using portable instruments –  Identification and differentiation of oil (including dilbit) from

background materials in-situ –  Infrared (FTIR) and fluorescence

•  Detection and monitoring of oil (including dilbit) in the water column

–  Towed fluorometers –  C-3 Turner


Response tools: Dispersant Effectiveness •  Two products tested so far: Access Western Blend (AWB)

and Cold Lake Blend (CLB) •  Dispersant effectiveness (Corexit EC9500A) determined by

the low-energy Swirling Flask Test & the high-energy Baffled Flask Test at temperatures from 5 to 25 °C

•  Dispersants were ineffective at all temperatures in the SFT, while the BFT had a positive response for most conditions

•  Estimated “Window of Opportunity” for dispersant effectiveness limited to <12 hrs at temperatures below 15 °C

“Dilbit” products have very short windows for application of oil spill dispersants.


Dispersants: Time Window-of-Opportunity

Time window-of-opportunity for Access Western Blend using Corexit EC9500A


Outputs to date

•  Publications –  Yang, C., Wang, Z., Yang, Z., Hollebone, B., Brown, C.E., Landriault, M., Fieldhouse, B.,

Chemical fingerprints of Alberta oil sands and related Products., (2011) Environmental Forensics, 12 (2), pp. 173-188

•  36th AMOP Technical Seminar on Environmental Contamination and Response, June 2013 :

–  Wang, Z., Yang, C., Yang, Z., Hollebone, B., Brown, C.E., Landriault, M., Fieldhouse, B., Liu, Y., Zhang, G., Hewitt, M., Parrott, J., Frank, R.A., Forensic source differentiation of petrogenic, pyrogenic, and biogenic hydrocarbons in Canadian oil sands environmental samples, (2013)

•  Federal Government Technical Report, 2014 –  Environment Canada, Fisheries and Oceans Canada, Natural Resources Canada,

“Properties, Composition and Marine Spill Behaviour, Fate and Transport of Two Diluted Bitumen Products from the Canadian Oil Sands”.

–  http://www.ec.gc.ca/scitech/6A2D63E5-4137-440B-8BB3-E38ECED9B02F/1633_Dilbit%20Technical%20Report_e_v2%20FINAL-s.pdf

•  EC Oil Properties Database


Outputs to date, continued

•  International Oil Spill Conference - Poster –  M. Goldthorp, P. Lambert and C. Brown, “Survey of Portable Oil Detection Methods”.

•  37th AMOP Technical Seminar on Environmental Contamination and Response, Canmore, AB June 2014

–  B. Fieldhouse, A. Mihailov, and V. Moruz, “Weathering of Diluted Bitumen and the Implications to the Effectiveness of Dispersants ”, pp. 388-352.

–  M. Goldthorp, B. Fieldhouse, P.G. Lambert, C. Yang, and C.E. Brown, “Oil Profiling Using Portable Instruments”, pp. 401-414.

–  S. Laforest, P.G. Lambert, J. Duffe, L. Gamble, B. Chaudhary, and C.E. Brown, “Studies on the Fate and Behaviour of Diluted Bitumen on Marine Shorelines”, pp. 415-427.

Future: •  Interspill 2015

–  B. Hollebone et al, Simulated Environmental Weathering Behaviours of Diluted Bitumen –  S. Laforest, P.G. Lambert and M. Goldthorp, The development of a shoreline oil spill R&D program for

diluted bitumen on marine shorelines •  38th AMOP Technical Seminar on on Environmental Contamination

and Response, BC


Ongoing work

•  Preparedness to support response to potential spills: –  Adding new oils to the oil properties and composition database

▪  Input to Spill models ▪  Oil forensics for spill monitoring

–  Pre-mapping continues in northern BC –  Testing of spill treating agents –  Spill modelling data (meteorology, hydrology, oil properties)

•  Research and development to support improved response –  New research on dilbit behaviours: weathering, dispersion,

sedimentation, shoreline “stickiness” and penetration –  Persistence to long-term breakdown –  Better response technologies and detection –  New physics for spill models.


Contact Information

Dr. Bruce Hollebone Emergencies Science and Technology Section

Environment Canada Email: [email protected]

Tel: (613) 998-9622

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